Synthesis of oxygenated organic compounds



July 10, 1951 J. K. MERTz'wElLLER Erm. 2,560,360

snmmsrs oF oxYGENATED ORGANIC coupounns med June 11, 1947 sePAnAToR 63 83 coNoEN'soR SCRUBl-:R 'l i] a5 ALKALmE g si; WER 132959 AouEous ILAYER 69 ,Tfsl-:TTLER l z neoensnnron $5/ 75 "new" Fmclonnon' l 25 oxo nEAcToR nu l 59 REMOVAL 60H12 791 "A-ET neon uns 2 l norous A/ es b loo |02 35 ruw. f zza-cf l los 99 T -=2=- L 95 j l f n on .I srcfmsz "lTMNIZIERW`i v /9' f 1 2 INVENTORS JOSEPH K. MERTZWEILLER JOHN J. OWEN ATTORNEY Patented July l0, 1951 SYNTHESIS F OXYGENATED ORGANIC COMPOUND Joseph K. Mettxwelller and John J. Owen, Baton Bouge, La., aeslgnors to Standard 0il Development Company, a corporation of Delaware Application June 11, 1947, Serial No. 753,978

Claims. (Cl. 26o-632) The present invention relates to the production of oxygenated organic compounds by the reaction of olens with hydrogen and carbon monoxide and more specically to the preparation of improved olefinic feed stocks for processes of this type. In particular, the invention refers to the production of oxygenated organic compounds from olens obtained by the catalytic conversion of carbon monoxide and hydrogen and to improvements in the preparation of such olens for the purpose of producing oxygenated organic compounds therefrom.

It is well known in the art that oxygenated organic compounds may be synthesized from olens or diolens by a reaction with carbon monoxide and hydrogen in the presence of catalysts containing cobalt, iron, nickel or thelike in a two-step process in which predominantly aldehydes and ketones and minor proportions of alcohols are formed in a rst step in the presence of the catalysts mentioned above and the product from the rst step is hydrogenated in a second step to convert aldehydes and ketones into the correspondingalcohols. The catalyst used in the rst stage may be employed in the second stage. However, other known hydrogenation catalysts may be used in the latter stage such as metallic nickel, nickel supported on kieselguhr, and others.

'I'he catalyst for the iirst stage usually contains promoters such as thoria, magnesia and the like.

The alcohols produced by this process normally contain one more carbon atom than the olefin used as the starting material, the position of -the added hydroxyl group depending on the positions of the double bond in the olens. The oleflns to be used as starting material may therefore he selected as a function of the purpose for which the product alcohol is desired.

For example, a detergent such as sodium lauryl sulfate may be prepared from an olen such as undecene-l by the alcohol synthesis. Other olens and diolens such as ethylene, propylene, butylene, pentenes, hexenes, butadiene, pentadienes, olen polymers. such as diisobutylene, triisobutylene, polybutylenes and olenic fractions from thermal or catalytic cracking operations and other sources may be used as starting material depending on the nature of the aldehydes and alcohols desired. The olens fed may comprise pure olens or hydrocarbon mixtures containing olens. In general, olens having from 2 to 18 carbon atoms and more particularly from 8 to 18 carbon atoms, in the molecule are preferred.

The synthesis gas mixture containing hydrogen and carbon monoxide may be produced from any conventional sources such as carbonaceous solids or gasesinanymannerknownperseandinany desired ratio of hydrogen to carbon monoxide.

Ratios of 0.5 volume of hydrogen to 4.0 volumes 'of hydrogen per volume of carbon monoxide may be employed, about 1.0 volume of hydrogen per volume of carbon monoxide being preferred. The reaction of the oleiins with H2 and CO is generalLv conducted at pressures in the range of about to 300 atmospheres and temperatures in the range of about F. to 450 F.

The quantity of Hz-l-CO with respect to olens used may vary within wide ranges, for example from 1000 to 45,000 cu. ft. of Hz-i-CO per barrel of olefin fed. In general, approximately 2,500 to 15,000 cu. ft. of Hz-i-CO per barrel of olen feed are employed. In the hydrogenation step temperatures are generally within the range of from about 150 F. to 450 F. while pressures within the range of about 100 to 300 atmospheres are suitable.

The catalysts for the rst stage of the process are usually employed in the form of salts of the catalytically active metal with high molecular weight fatty acids such as stearic, palmitic, oleic, naphthenic, linoleic. and similar acids of natural or synthetic origin. For example, metal soaps such as cobalt stearate, nickel oleate, cobalt naphthenate, and iron linoleate are suitable catalysts. These salts are soluble in the liquid olefin feed and may be supplied to the reaction zone in the form of hydrocarbon solutions or dissolved in the olen feed.

Prior to the present invention, attempts have been made to utilize as starting materials for the process described above, olefins produced by the catlytic conversion of carbon monoxide with hydrogen over catalysts such as iron promoted with alkali metal compounds, or similar promoters. However, these attempts have not been successful because olefin conversion in the rst olen oxygenation stage and selectivities toward the formation of alcohols are so low that the process based on synthetic olei-lns of this type becomes uneconomical. It is the principal object of the present invention to provide a procedure by which this diiliculty may be overcome and synthetic olens may be converted into useful starting materials for the production of oxygenated organic compounds by the conversion of such olens with carbon monoxide and hydrogen.

Our investigations have indicated that the difculties arising in connection with the use of synthetic olefins as starting materials for the production of oxygenated organic compounds are connected with the presence of certain oxygenated compounds particularly acidic materials introduced into these olens by the original synthesis reaction. Therefore, the invention relates in its broadt aspect to the production of oxygenated organic compounds from synthetic olefins which have been subjected to a treatment adapted substantially completely to free said oleiins of synthetic acidic materials.

More specifically, the process of the invention comprises a treatment of synthetic olens with the hydroxides or oxides of the alkali or alkaline earth metals whereby acidic constituents are removed from the oleiins, and the use of the thus purified olefins for the production of oxygenated organic compounds by the catalytic reaction with carbon monoxide and hydrogen. The alkaline treating materials may be employed in solution or in solid form at normal atmospheric or elevated temperatures. For example, caustic soda solutions of 1 to 20 per cent. preferably 3 to 15% are suitable for the purposes of the invention at treating temperatures of about 50 to 300 F. preferably about 50 to 100 F. It has been found that the yields of oxygenated organic compounds and the alcohol selectivities of the process using synthetic olens alkali-treated in accordance with the present invention are satisfactory for commercial operation.

-rThe present invention will be best understood from the more detailed description hereinafter wherein reference will be made to the accompanying drawing, the single figure of which is a schematical illustration of a system suitable for carrying out a. preferred embodiment of the invention.

Referring now in detail to the drawing, the numeral indicates a conventional fluid type catalytic synthesis reactor for the conversion of carbon monoxide with hydrogen in the presence of finely divided synthesis catalyst. Reactor 5 contalns a dense turbulent fluidized mass 3 of a synthesis catalyst, preferably an iron catalyst such as sintered pyrites ash promoted with about 1.5 per cent of potassium fluoride. Synthesis feed gas containing carbon monoxide and hydrogen is supplied from line I to reactor 5 at a suitable synthesis pressure of 5 to 50 atmospheres, preferably to 40 atmospheres. The synthesis temperature may be maintained within the approximate limits of 500 to 800 F., preferably between about 550 and 700 F. by conventional methods of heat removal (not shown). Other details of the operation of fluid synthesis reactors using iron catalysts are well known and need not be further specified here.

The total product of the synthesis reaction is withdrawn from reactor 5 through line 1 and passed to a conventional gas solids separator 9 wherein entrained catalyst nes may be separated from the product vapors and gases and returned through return pipe II to the catalyst mass 3 in reactor 5. Product vapors and gases substantially free of entrained catalyst are passed through line I3 to a separator I5 wherein the separation of liquids and gases and of a hydrocarbon layer from an aqueous layer is accomplished by cooling and settling. Gas is withdrawn overhead through line I1 to be either recycled to reactor 5 or passed to a conventional gas recovery plant (not shown). 'I'he aqueous layer containing the water-soluble oxygenated products is withdrawn from the bottom of separator I5 through line I9.

The total liquid hydrocarbon oil product containing olens and oil-soluble organic compounds is withdrawn from an upper liquid layer within separator I5 and passed through line 2I to a conventional fractionating column 23. The hydrocarbons are fractionated in column 23 so as to recover heavy bottoms withdrawn through line 25 and an oleilnic fraction of the boiling range desired for the production of oxygenated organic compounds. This fraction preferably has a relatively narrow boiling range of about 50 to 100 F. falling within the approximate limits of to 600 F., preferably 250 to 400 F., depending on the molecular weight and character of the oxygenated compounds desired as the final product of the process.

The overhead from fractionator 23 passes through line 21 to `a condenser 29 and from there in liquid form through line 3| to the alkali treating chamber 35. The treating chamber 35 preferably contains a porous packing of refractory materials or the like such as Raschig rings, Berl saddles, etc. An alkaline solution of the desired strength is supplied to treating chamber 35 from alkali storage tank 31 through lines 38 and/or 4I. Treating chamber 35 is preferably maintained at a temperature of 50 to 300 F. and may be operated at any desired pressure. On thir way through treating chamber 35 the olefinic feed and the alkaline treating solution are thoroughly mixed in any conventional manner and intimately contacted so as to assure substantially complete removal of the acids contained in the hydrocarbon feed in the form of organic salts of the metal of the alkaline treating agent.

A mixture of treated hydrocarbons and spent treating agent is withdrawn from treating chamber 35 through line 43 and passed to a settler 45 wherein it is separated into an aqueous bottom layer and oil top layer. The aqueous bottom layer containing excess alkaline treating agent and organic salts of its metal is withdrawn through line 41 and passed to an organic acid regenerator 43 wherein it is treated with a strong inorganic acid, preferably sulfuric acid to set free the organic acids. The acid mixture is passed from regenerator 49 through line 50 to a settler 5I wherein it is separated into a top layer containing the crude organic acids which may be withdrawn through line 53 and a bottom layer containing the neutral organic salt produced in regenerator 49. The bottom layer may be discarded through line 55.

Returning now to settler 45 the hydrocarbon layer is withdrawn through line 51 and dried in drier 59 with conventional drying agents such as calcium chloride, alumina, or other dehydrating agents and/or adsorbents.

The dried liquid olenic hydrocarbons pass from drier 59 through line 6I to a pipe 63 wherein they are mixed with a catalyst promoting the conversion with carbon monoxide and hydrogen'into oxygenated organic compounds. Any conventional type catalyst such as cobalt stearate or naphthenate may be used in proportions varying between about 0.1 and 5.0 per cent by weight of olens. The mixture of olefinic feed stock andv catalyst is passed to an upper portion of primary reactor 65 to be converted into oxygenated organic compounds primarily aldehydes and ketones.

Simultaneously, a gas mixture containing hycatalyst in the form of metal carbonyl, and preferably recycled through line 13 to gas feed line 61 Liquid oxygenated reaction products and unreacted olefins are withdrawn from a bottom portion of reactor 65 through line l5 and passed to a catalyst removal zone 11 which is packed with a catalytically inert solid material such as ceramic Raschig rings, kieselguhr, pumice, charcoal or silica gel, etc. Hydrogen recovered from a later stage of the process, as will appear hereinafter, may be supplied to zone l1 through line 79 and passed through zone 'I1 countercurrently to the liquid oxygenated product. Catalyst removal zone 11 is preferably maintained at a temperature of about 200 to 450 F. at which the catalyst which enters zone '|1 predominantly in the form of metal carbonyl dissolved in the liquid product is decomposed into metal and carbon monoxide. The metal is deposited on the inert packing within zone 'Il while the carbon monoxide is purged by the hydrogen. A mixture of hydrogen and carbon monoxide is Withdrawn through line 8| either to be discarded through line 83 or to be passed through line 85 to a methanizer 8l wherein the carbon monoxide is converted thermally or catalytically into methane in any conventional manner. The methane and hydrogen may be passed through line 89 to hydrogenation reactor 95.

'Ihe liquid oxygenated product now free of oxygenation catalyst is withdrawn from zone 11 through line 9| and passed to a bottom portion of hydrogenation reactor 95. Simultaneously, hydrogen is supplied to reactor 95 through line 93 in proportions suflicient to convert the aldehydes and ketones contained in the oxygenated feed into the corresponding alcohols. Reactor 95 contains a mass 91 of any conventional hydrogenation catalyst. For example, when nickel is employed as the hydrogenation catalyst, reactor 95 may be operated at pressures ranging from about 300 to 3000 pounds per square inch, at temperatures of about 300 to 400 F. and at an H2 rate of about 5000 to 20,000 normal cu. ft. per bbl. of feed. The catalyst may be employedin the form of xed or moving beds, or it may be suspended in the liquid feed. Details of hydrogenation processes of this type are well known in the art and need not be further specified. Unreacted hydrogen may be withdrawn overhead from reactor 95 through line 99 and either Vented through line or recycled through line |02 via lines 'I9 and/or |03 to the catalyst removal zone 11, as previously described, or hydrogenation reactor 95.

The hydrogenated product stream is withdrawn from reactor 95 through line |05. This product which is now highly concentrated in the desired alcohols may be passed to any conventional product recovery plant (not shown) The system illustrated by the drawing permits of various modications. Fixed or moving bed reactors may be used in place of uid synthesis reactor in any manner known per se. Other synthesis catalysts promoting the formation of liquid olefms from carbon monoxide and hydrogen may replace the iron catalysts specified. The alkaline treating agent in treating chamber 35 may be solid rather than a liquid. Other conventional oxygenating catalysts than those specied may be supplied to line 63. For example, insoluble nely divided metal catalysts may be used in aqueous or oil suspension. Instead of nickel, other hydrogenation catalysts such as tungsten, or suldes of metals of groups VI and Ally VIII of the periodic table may be utilized. Fur ther modifications may occur to those skilled in the art without deviating from the spirit of the invention.

The invention will be further illustrated by the following specic examples.

Eample I Inspection of this fraction showed the follow-l ing values:

Gravity, A. P. I. l 53.4 Hydroxyl number 9 Carbonyl number 274 Saponication number 42 Acid number 32.8

Bromine number 92 A sample of this fraction was treated with 5 per cent caustic soda solution at '70-90 F. for 12 minutes. The treated product showed the following inspection data:

Gravity, A. P. I. 56.5

Hydroxyl number 23 Carbonyl number 33 Saponication number 11A Acid number 0.9 Bromine number 88 The estimated olen content was changed from about 73% in the untreated fraction to about 70 per cent in the treated fraction.

A sample of the untreated fraction was reacted in an autoclave with CO and H2 at the conditions and with the results given below using a catalyst consisting of 31.2% Co, 0.9% Cu, 5.6% Th02, 62.3% silica.

Aldehyde stage Catalyst concentration, wt. per cent 11 Volume ratio Hz/CO in gas 1.2 Duration of test, hours 5 Temperature, F. l 275 Pressure, p. s. i. g. 3000 Olefln conversion, wt. per cent 16 Gravity of product, A. P. I 49.8

Because of the extremely low yield of oxygenated product the latter was not subjected to hydrogenation.

A sample of the alkali treated fraction was converted using the same catalyst at the conditions and with the results given below:

Aldehyde Hydrogen- Stage ation Stage Catalyst Concentration, Wt. Per Cent 12 t l 20 Volume Ratio Hz/CO In Gas l. 2 Duration of Test Hours--- 5 12 Temperature, l. 275 350 Pressure, p. s. i. g 3,000 2, 700 Olen Conversion, Wt. Per Cent 86 Inspection of Product:

Gravity, A. P. I 37.3 Hydroxyl Number 35 210 Carbonyl Number 197 l 1 Nickel on kieselguhr used as catalyst in hydrogenaton stage.

Bromine number A comparison oi the results reported above indicates that the treatment of the synthetic oleiins with alkali in accordance with the present invention leads to about a -fold increase in olefin conversion.

Example Il l A synthetic oleiln traction boiling between 350 and 400 F. was obtained from an oil produced as A sample of this fraction was treated with a per cent caustic soda solution at a temperature of 7090 F. for 12 minutes. The treated sample showed the following inspection data:

Gravity, A. P. I.. 44.3

Hydroxyl number L 17 Carbonyl number 33 Saponiilcation number 13 Acid number 0.1 Bromine number 57 Aldehyde stage talyst concentration, wt. per cent 11 olume ratio, Hz/CO in gas 1.2

' Duration oi' test. hours 5 Temperature, F 350 Pressure, p. s. i. g 3000 .Olen conversion, wt. per cen 6 Gravity of product, A. P. I. 40.4

The small amount of oxygenated product formed was not hydrogenated.

The treated sample was oxygenated usingvthe same catalyst at the conditions and with theresults given below.

ence oi.' an oxygenation catalyst at oxygenation While the the foregoing description and exemplary operations have served to illustrate speciiic applications and results of the invention. other modications obvious to those skilled in the art are within the scope of the invention. Only such limitations should be imposed on the invention as are indicated in the appended claims.

We claim:

1. The process oi producing oxygenated organic materials which comprises subjecting to a treatment with an alkaline treating agent oleiins produced by the catalytic conversion of C0 with H: in the presence of a hydrocarbon synthesis catalyst, said treatment being adapted to remove acidic materials from said oleilns. and contacting said treated olens with Hz and C0 in the presconditions to produce oxygenated organic materials.

2. The process of claim 1 in which said treating agent comprises caustic alkali.

3. The process of claim 1 in which said treating agent comprises a compound selected from the group consisting of the oxides and hydroxides of the alkaline earth metals.

4. The process of claim 1 in which said alkaline treating agent is in the form of an aqueous solution.

5. The process oi claim 4 in which said solution contains about :fl-15% oi NaOH.

6. The process of claim 1 in which said oleilns are treated with said treating agent at temperatures of 50 to 300 F.

A7. The process oi claim 1 in which said oxygenated materials are hydrogenated in the presence of a hydrogenation catalyst and at hydrogenation conditions oi temperature and pres` sure conducive to the conversion of aldehydes and ketones contained in said materials into the corresponding alcohols.

8. The process oi claim 1 in which said hydrocarbon synthesis catalyst is an iron-type catalyst and said catalytic conversion is carried out-at temperatures of about 500-800 F. and pressures of about 5-50 atmospheres. L

9. The process oi .producing oxygenated organic materials which comprises contacting a gas mixture containing CO and H2 in synthesis proportions at synthesis conditions of temperature and pressure with a synthesis catalyst promoting the formation of normally liquid olenic hydrocarbons at said synthesis conditions, recovering synthetic olefins, treating said recovered olens with anvalkaline treating agent at conditions adapted to neutralize organic acids contained in said oleilns to form organic salts, separating said salts from said oleins, contacting said separated oleilns with CO and H2 at Oxygenation conditions of temperature and pressure and in the presence of an oxygenation catalyst.

. adapted to convert said olens into oxygenated Aldehyde Hyd'iogen' Stage sagg,

Catalyst Concentration, Wt. Per Cent 9 9 Volume Ratio of Hz/CO in Gas 1. 2 Duration oi Test, Hours 5 l2 Temperature, F.-. 350 350 60 Pressure, p. s. i'. g... 3, 000 2, 700 Oleiln Conversion, Wt. Per Cent 77 Inspections of Product:

Hydroxyl Number 156 Carbonyl Number 2 l The oxygenation catalyst was used in the hydrogcnation stage.

A comparison oi' the above results shows that the alkali treatment of these synthetic oleiins in accordance with the present invention permits about a 13fold increase of the oleiin conversion into oxygenated products.

It should be understood that the slight deviations in the oxygenation conditions oi' the experiments reported above have little or no iniluence on oleiin conversion.

compounds, and recovering said oxygenated compounds.

10. The process of claim 9 in which said synthesis catalyst is an iron-type catalyst, said synthesis temperature is about 500-800 F., said synthesis pressure about 5-50 atmospheres, and said synthesis proportions about 0.5-3 volumes of Hz per volume of CO.

11. The process of claim 9 in which said separated olens are'dried prior to their contact with said CO and Hz.

12. The process of claim 9 in which said salts' are converted with a strong inorganic acid into organic acids and inorganic salts of said inor- 9 10 ganic acids; and said organic acids are recovered. UNITED STATES PATENTS 13. The process of claim 9 in which said syn- Number Name Date product of said synthesis reaction. 1 984 884 Lazier Dec 18 1934 14. The PI'OCBSS 0f Claim 13 in Which Said dS" 2,171,324 zetzsehemtl Aug. 29, 1939 tilled synthetic olens have a boiling range be- 5 2327'066 Roelen Aug, 17 194:3r thetic olens are recovered by distilling the total 2360787 Murphree t a1 n" Oct 17 1944 tween about 200 to about 600 F.v 437' 0o e h 9 1 4 15. The processl of claim 14 in which said bou- 2 6 Gr s am et al' "if" Mar' 9 8 ing range is a narrow range of about; 50-100 F. OTHER REFERENCES falling within the broad range of from about; 250 l0 Brennsi-,omchemie' VOL 16J Ne 20 (1935) pages 11 about 400 F- v e 382-387 (article by Koch et al.

A U. S. Naval Technical Mission in Europe. ggf? (WIIRTZWEILLER' Technical Report No. 24a-45, The synthesis of .v Hydrocarbons and Chemicals from CO and H2,"

REFERENCES CITED 15 pages 29, 30, 118 and 119. September 1945.

Reiiner and Natural Gasoline Manufacturer, The following references are of record in the v01, 17l No, 2, February 1933, page 50 (article le of this patent: e by Naphta1i) 

1. THE PROCESS OF PRODUCING OXYGENATED ORGANIC MATERIALS WHICH COMPRISES SUBJECTING TO A TREATMENT WITH AN ALKALINE TREATING AGENT OLEFINS PRODUCED BY THE CATALYTIC CONVERSION OF CO WITH H2 IN THE PRESENCE OF A HYDROCARBON SYNTHESIS CATALYST, SAID TREATMENT BEING ADAPTED TO REMOVE ACIDIC MATERIALS FROM SAID OLEFINS, AND CONTACTING SAID TREATED OLEFINS WITH H2 AND CO IN THE PRESENCE OF AN OXYGENATION CATALYST AT OXYGENATION CONDITIONS TO PRODUCE OXYGENATED ORGANIC MATERIALS. 